The　rich　phase　behavior　of　block　copolymers　(BCPs)　has　drawn　great　attention　in　recent　years.　However,　the　double　diamond　(DD)　phase　is　rarely　obtained　because　of　the　competition　between　the　minimization　of　interfacial　energy　and　packing　frustration.　Here,　a　rod-coil　BCP　containing　mesogen-jacketed　liquid　crystalline　polymer　is　designed　to　acquire　ordered　bicontinuous　network　nanostructures.　The　reduction　of　internal　energy　originating　from　the　orientational　interaction　among　the　rod　blocks　can　compensate　for　the　free　energy　penalty　of　packing　frustration　to　stabilize　the　DD　structure.　The　resulting　BCP　can　also　experience　lamellae-to-DD　and　double　gyroid-to-lamellae　transitions　by　changing　the　annealing　temperature.　These　results　make　the　rod-coil　BCP　an　excellent　candidate　for　the　self-assembly　of　ordered　network　structures,　demonstrating　great　potential　in　nanopatterning　and　metamaterials.　©　Chinese　Chemical　Society　Institute　of　Chemistry,　Chinese　Academy　of　Sciences　2024.